Cyclic amidines



United States Patent This invention deals with specific cyclic new compositions of matter.

The cyclic amidines of the present invention may be represented by the formula amidines as in which R is alkyl of 1 to 24 carbon atoms or phenyl, naphthyl, benzyl or alkyl substituted phenyl, naphthyl or benzyl in which the total alkyl substituents contain up to 16 carbon atoms; R is hydrogen or alkyl of 1 to 24 carbon atoms, collectively R and R may form a ring with the nitrogen atom to which they are joined, namely morpholino, thiamorpholino, piperidino and pyrrolidinyl, X is ethenylene, ethylene, alkyl or alkenyl substituted ethylene having a total of up to 20 carbon atoms, a 1,2-cyc1ohexylene or alkyl substituted 1,2-cyclohexylene having a total of up to 16 carbon atoms, 1,2-cyclohexenylene or alkyl substituted l,2-cyclohexenylene having a total of up to 16 carbonatoms, 3,6-methano-1,2-cyclohexylene and 3,6-methano-1,2-cyclohexenylene; R is hydrogen, Z-hydroxyethyl, 2-aminoethyl, 2 or 3-hydroxy propyl, 2 or 3-aminopropyl, 2 or 3-(2-aminoethyl)aminopropyl, 2 or 3-(2 or 3-aminopr0pyl)aminopropyl or 2- '(Z-aminoethyl)aminoethyl, and D is a divalent saturated chain of 2 to 3 carbon atoms whose available valences are satisfied by hydrogen atoms or alkyl groups having a total of up to 12 carbon atoms and combinations of hydrogen and alkyl groups having a total of up to 12 carbonatoms or 1,2-cyclohexy1ene.

Typically R represents methyl, butyl, octyl, dodecyl, octadecyl, tetracosyl, phenyl, naphthyl, benzyl, octylphenyl, butylnaphthyl and octylbenzyl.

Typical embodiments of R include hydrogen, methyl, butyl, octyl, dodecyl, octadecyl, eicosyl and tetracosyl.

Typical embodiments of X include ethylene, ethenylene, dimethylethylene, octylethylene, dodecylethylene, dodecylbutylethylene, dodecenylethylene, 'cyclohexylene, methylcyclohexenylene, octylcyclohexenylene and 3,6-methan- 1,2-cyclohexenylene.

Typical embodiments of the symbol D include ethylene, dimethylethylene, butylethylene, octylethylene, propylene, dimethylpropylene, butylpropylene, octylpropylene and 1,2-cyclohexylene.

A particularly effective embodiment of the above cyclic amidines includes either R or R as a tertiary alkyl group,

- that is, an alkyl group having the configuration in which A represents alkyl groups that total from 3 to 23 carbon atoms, preferably from ll'to 23 carbon atoms.

group or mixtures of alkyl groups within the stated carbon content range. Commercially available compounds that provide this part of the molecule are known to contain mixtures of alkyl groups. Particularly outstanding amidine product.

in this respect are those in which either R or R represents a mixture .of tertiary alkyl groups containing 12 to 15 carbon atoms averaging 13 carbon atoms or a mixture of 18 to 24 carbon atoms.

'Especially outstanding embodiments are those in which R represents tertiary alkyl of 4 to 24 carbon atoms, phenyl or benzyl, R is hydrogen or alkyl of 4 to 24 carbon atoms, X is ethylene, ethenylene, dodecenylethylene or 1,2-cyclohex-4-enylene,- R is hydrogen, hydroxyethyl, or aminoethyl and D represents ethylene.

The cyclic amidines of the present invention are prepared by reacting a compound having the formula with one having the formula R NHDNH at the reflux temperature of the reaction system. It is possible to conduct the reaction without a solvent or if a solvent is preferred, which is generally the case, one may employ an inert aromatic compound such as benzene, toluene, xylene, or the like. Toluene and xylene are preferred, particularly with the higher molecular weight reactants. The reaction is conducted at the boiling point of the reaction system and is continued until two moles of Water per mole of acid are removed. The water is removed from the reaction mixture as the reaction progresses either by distillation or when a solvent is employed, by an azeotropic distillation. The reagents are employed in equi molecular quantities or, if desired, an excess of the amine may be used. If excess amine is employed in order to assure highest yields, the excess may be removed by distillation such as under reduced pressure or small amounts of excess amine need not be removed since it does not interfere'with the functioning and utility of the cyclic Yields of the cyclic amidine product are consistently in excess of and frequently approach a quantitative result.

Typical embodiments of the amine reactants include ethylenediamine, diethylenetriamine, triethylenetetramine, hydroxyethylethylenediamine, propylenediarnine, dipropylenetriamine, tripropylenetetraamine, hydroxyethylpropylenediamine. Typical embodiments of'the amidoacid reactants include N-butylmaleamic, N-octylmaleamic, N dodecylmaleamic, N-octadecylmaleamic, N-benzylmaleamic, N-phenylmaleamic, N-naphthylmaleamic, N-butylsuccinamic, N,N-dioctylsuccinamic, N-octylsuccinamic, N-dodecylsuccinamic, N-octadecylsuccinamic, N-phenylsuccinamic, N-benzylsuccinamic, N-butyldodecenylsuccinamic, N-octylcumylsuccinamic, N-octyloctenylsucinamic, N-phenyldodecenylsuccinamic, N-t-dodecyltetrahydrophthalamic, N-butyltetrahydrophthalamic, N-octadecyltetrahydrophthalamic, N-dodecyl 3,6 methanotetrahydrophthalamic and N-octyltetrahydrophthalamic acids.

The cyclic amidines of this'invention are useful fungicides. They are particularly effective against Stemphylium sarcinaeforme, Alternaria solani and 'Monilinia fructicola when applied according to standard techniques. Effective amounts range from 5 to p.p.m., preferably 10 to 50 ppm. i

The present products, when incorporated into distillate fuels, impart carburetor anti-icing activity, carburetor detergency, anti-rust activity and sludge dispersancy, when used in amounts of about 0.001 to 2.0% by weight, preferably 0.005 .to 1.0% by Weight.

It is to be understood that the distillate fuels contemplated are those that boil from about 75 to 750 P. which includes gasolines, jet and diesel fuels and furnace oils. The present compounds are particularly useful in fuels that boil up to about 600 F., that is, the normal to evaluate the stalling characteristics of a fuel.

gasolines and jet fuels. The need for an additive to supply the above enumerated properties is widely recognized in the art since lack of such activity and combinations thereof in distillate fuels leads to a marked diminution of commercial value of such distillate fuels.

The compounds of the present invention were subjected to a standard carburetor anti-icing test which is a test The test employed a 1957 Buick engine, equipped with a factory radiator, manifold, carburetor, and an automatic choke. The motor parts are stabilized at 40:4" F; The test was conducted at 40:4 F. and 90% humidity. The motor was accelerated to 1500 r.p.m. for one minute and then reduced to idle for 30 seconds. If the engine stalled, such was recorded and the engine was immediately re-started, accelerated to 1500 r.p.m. for one minute and then reduced to idle for 30 seconds. If stalling did not occur during the 30 seconds idle time, the speed of the motor was accelerated to 1500 r.p.m. and the cycle was repeated. This was continued until the engine was completely warmed up and the number of stalls was recorded. In this test, the base fuel, resulted in nine stalls. With as little as 0.02% by weight of a compound of the present invention the number of stalls was reduced at least by 33 /s%. Particularly outstanding in this test is the compound of this invention wherein R represents tertiary octadecyl, R is hydrogen, X is ethenylene, D is ethylene and R is Z-aminoethyl.

The present compounds were evaluated in a standard carburetor detergency test in which there was employed a 1954 model 6-cylinder Plymouth engine. The carburetor was equipped with a clear plastic throttle body. The crankcase blowby from the engine was returned to the carburetor air inlet. The engine was operated on a base fuel under cyclic conditions for one hour to build up a black deposit on the carburetor until the throttle of the carburetor was 40% covered with black deposits. There was then incorporated into the same base fuel one of the cyclic amidines of the present invention in order to provide a composition of this invention. The test was then continued for an additional hours. The evaluation was based on the black deposit that remained after clean-up. Commercially available compositions reduce black deposits to 3236%. the present invention reduced the black deposits to 34% even when there was employed only 0.02 gram of a cyclic amidine of the present invention per 100 ml. of fuel. Particularly outstanding in this respect was a composition of the present invention containing the cyclic amidine wherein R represents tertiary octadecyl, R is hydrogen, X is ethenylene, D is ethylene and R is Z-aminoethyl.

The compounds of the present invention were subjected to an anti-rust test, ASTM D-665, Procedure A for distilled water, modified to use isooctane at 75 F. for a period of 24 hours. The base fuel itself gave a result of 100% rust. The compounds of the present invention when used in amounts as low as 0.01 gram per 100 ml. of the base fuel gave no rust at all. standing in this test were the compounds of the present. invention in which R is tertiary octadecyl, R is hydrogen, X is ethenylene or ethylene, D is ethylene and R is hydrogen, Z-hydroxyethyl or 2-aminoethyl.

The compounds of the present invention were subjected to a sludge dispersancy test as described by F. L. Nelson, D. P. Osterhout and W. R. Schwindeman, 1nd. Chem. 48, 1892 (1956). The test consists of preparing a liter of fuel oil containing a candidate additive for sludge dispersancy. In the same fuel oil composition there is incorporated four grams of synthetic sludge. The oil is then circulated for one hour through a single stage oil burner pump containing a 100-mesh strainer. The sludge deposit on the strainer is collected and weighed. The fuel oil without any additive led to an accumulation of sludge of 250 mg. The use of commercially acceptable sludge dispersants lead to less than 100 mg.

The compositions of Particularly out- D were ethylene and 1,3-propylene.

of sludge accumulation. The compounds of the present invention when employed in amounts of 0.01 to 0.02 gram per ml. of fuel oil gave sludge accumulations of less than 40 mg. down to 2 mg. Particularly effective in this test were those compounds wherein R represents a mixture of tertiary alkyl groups, on the one hand, having between 12 and 15 carbon atoms, averaging 13 carbon atoms, and, onthe other hand, having from 18 to 24 carbon atoms and a neutral equivalent of about 300 to 340. Outstanding results were also obtained when R represented hexadecyl, octadecyl or tertiary butyl. Outstanding embodiments of R were hydrogen, hexadecyl and octadecyl. Particularly effective embodiments of X were ethylene, ethenylene, cyclohexenylene and dodecenylethylene. The most effective embodiments of Outstanding results were obtained when R represented hydrogen, 2-hydroxyethyl or 2-aminoethyl.

The present invention may be more fully understood from the following examples which are offered by way of illustration and not by Way of limitation. Parts by weight are used throughout.

Example .1

A solution of N-t-octadecylmaleamic acid (215 parts) and diethylenetriamine (51.5 parts) in 350 parts of xylene is heated to reflux and the evolved water removed by azeotropic distillation. After 12 hours of refluxing 18 par-ts of water and 1.5 parts of excess amine are re moved. The solvent is then removed under reduced pressure and the product obtained as the residue. The product contains 10.3% nitrogen (theoretical 11.3%) and is identified as the compound of the present invention wherein R is a mixture of tertiary alkyl groups averaging 18 carbon atoms, R is hydrogen, X is ethenylene, D is ethylene and R is 2-aminoethyl.

Similarly a compound of the present invention is prepared exactly as above except that R represents hydroxyethyl. The product contains 8.2% nitrogen (theoretical 8.4%) and had a neutral equivalent of 485 (theoretical 498).

Example 2 A solution of N,N-dihexadecylmaleamic acid (269 parts) and diethylenetriamine (55 parts) in 400 parts of xylene is refluxed for 3 hours during which time 18 parts of Water is azeotropically removed. The xylene is removed leaving a residue of 307 parts of a product which is identified as the cyclic amid-inc of this invention in which R and R are hexadecyl, X is ethenylene, D is ethylene and R is Z-aminoethyl. The product contains 8.6% nitrogen (9.3% theoretical).

Similarly there is prepared a product of this invention wherein R and R are octadecyl, X is ethenylene, D is ethylene, R is Z-aminoethyl and contains 7.1% nitrogen (8.0% theoretical).

Example 3 A solution of N-t-octadecylmaleamic acid (43.6 parts) and ethylenediamine (6.0 parts) in 86 parts of xyleneis heated to reflux and the water removed as an azeotropic mixture. After two hours 2.2 parts of aqueous layer has been removed and 3.0 parts of ethylenediamine is added. Refluxing is resumed for three hours after which time a total of 5.0 parts of aqueous layer containing 3.0 parts of water and 2.0 parts of amine has been removed. The xylene is then removed by vacuum distillation leaving 48 parts of product as the residue. The product contains 9.2% nitrogen (9.1% theoretical). The product is a cyclic amidine in which R is tertiary octadecyl, R is hydrogen, R is hydrogen, D is ethylene and X is ethenylene.

Similarly there is prepared a product of this invention having the same structure as that above except that R represents tertiary octyl.

nitrogen (13.5% theoretical).

Example 4 There are mixed together 29.1 parts of N-t-tridecylmaleam-ic acid (in which the tridecyl represents a mixture of tertiary alkyl groups of 12 to 15 carbon atoms having an average of 13 carbon atoms) and 10.3 parts of diethylenetriamine. The temperature rises to about 80 C. and the mixture is then heated up to 155 C. over a period of 2% hours under a slow stream of nitrogen. Water is distilled oil and the heating discontinued. The mixture is cooled to about 100 C. and the remainder of water removed. A total of 3.8 parts of distillate is collected containing 0.5 part of amine. The product is recovered as a residue amounting to 35.1 parts and contains 14.2% nitrogen (15.6% theoretical). The product has a neutral equivalent of 208 (179 theoretical). The product is a cyclic amidine in which R is tertiary tridecyl, R is hydrogen, R is Z-aminoethyl, X is ethenylene and D is ethylene.

In a similar way, similar products of the present invention are prepared which have the same structure as above except that when R represents hydrogen the product contains 12.7% nitrogen (13.3% theoretical) and has a neutral equivalent of 298 (315 theoretical) and when R represents 2-hydroxyethyl the product contains 10.6% nitrogen (11.6% theoretical).

Example 5 A mixture of N-t-octadecyltetrahydrophthalamic acid (94.8 parts) and diethylenetriamine (20.6 parts) is refluxed in 367 parts of xylene for five hours. The Water evolved is removed by azeotropic distillation. After five hours an additional 2.8 parts of diethylenetriainine is added and refluxing continued for 24 hours. The xylene is removed under reduced pressure and the product is recovered as the residue. The product is a cyclic amidine of this invention in which R represents an alkyl group having a tertiaryalkyl structure and containing an average of 18 carbon atoms, R is hydrogen, X is cyclohexenyl, D is ethylene and R is aminoethyl. The product contains 9.0% nitrogen (10.3% theoretical).

Similarly there are prepared the products of this invention wherein "R represents a mixture of tertiary alkyl groups of 12 to 15 carbon atoms averaging 13 carbon atoms, R is hydrogen, X is cyclohexenyl, D is ethylene, and R is hydrogen, 2-hydroxyethyl or 2-arn-inoethyl. When R is Z-aminoethyl the product contains 12.8% When R is 2-hydroxyethyl the product contains 1 1.9% nitrogen (11.3% theoretical).

All are excellent distillate fuel additives.

Example 6 A solution of N-t-octadecylsuccinamic acid (216 parts) and hydroxyethylenediamine (52 parts) in 367 parts of xylene is refluxed. The water that is formed is removed as an azeotropic mixture over 15 hours. The aqueous layer contains 1.3 parts of amine. The xylene is removed under reduced pressure leaving 260'parts of product as the residue. The product contains 7.6% nitrogen (7.6%

It has aneutral equivalent of 497 (500 Similarly, a product is prepared as above wherein R represents am-inoethyl and contains 9.1% nitrogen (9.2% theoretical) In like manner there are prepared the cyclic amidines of the present invention wherein R represents a mixture of tertiary alkyl groups containing 12 to 15 carbon atoms, averaging 13 carbon atoms, R is hydrogen, X is ethylene, D is ethylene. When R is 2-aminoethyl the product has a neutral equivalent of 189 (180 theoretical). When R represents 2-(2-aminoethy1)aminoethyl the product contains 15.7% nitrogen. When R is hydrogen the product contains 12.7% nitrogen (13.2% theoretical) and has a neutral equivalent of 298 (315 theoretical).

All are useful additives for distillate fiuels.

Example 7 A solution of N-t-hutyldodecenylsuccinarnic acid (67.8 parts) and a diethylenetriamine (20.6 parts) in 200 parts of xylene is refluxed for 8 hours during which time the water is removed as an azeotropic mixture. An additional 2.3 parts of diethylenetriamine is introduced and refluxing is continued for an additional five hours. A total of 8.3 parts of aqueous layer is separated. The reaction mixture is stripped leaving the product as a residue of 72 parts. The product has a neutral equivalent of 205 (203 theoretical). The product is the cyclic amidine of this invention wherein R is tertiarybutyl, R is hydrogen, X is dodecenylethylene, D is ethylene, R is 2-aminoethy1.

In like manner a. similar product is prepared in which R represents a mixture of tertiary alkyl groups containing from 12 to 15 carbon atoms, averaging 13 carbon atoms, R is hydrogen, X is dodecenylethylene, D is ethylene and R is hydrogen.

Example 8 Example 9 A solution of N-phenyl-u-dodecenylsuccinamic acid (36 parts, 0.1 mole) and diethylenetriamine (10.3 parts, 0.1 mole) in xylene parts) is heated at reflux for a total of 21 hours while water is removed azeotropically. A total of 3.7 parts of aqueous layer is collected containing 3.1 parts of water. The xylene solvent is removed under vacuum. This also removes some aniline which is displaced during the reaction. The residue has less than 3% acid as determined by titration with alcoholic potassium hydroxide. The neutralization equivalent of the residue is 223 (theoretical 213). The product is a cyclic amidine in-which R is phenyl, R is hydrogen, R is Z-aminoethyl, X is dodecenylethylene and D is ethylene.

A similar product is prepared where R is t-octyl.

Example 1 A mixture of N-t-octylsuccinamic acid (22.9 parts, 0.1 mole) and diethylenetriamine (10.3 parts, 0.1 mole) in parts xylene is heated to reflux for 12 hours. Water is removed azeotropically. The aqueous layer which collected in the water separator weighs 3.7 parts and contains 3.3 parts of water. The xylene is removed from the reaction mixture by distillation up to about 80 C. at 20 mm. of mercury. The residue (27.4 parts) has a neutralization equivalent of 147 and contains 18.1% nitrogen (theoretical 18.9%). which R is t-octyl, R is hydrogen, R is Z-aminoethyl, X is ethylene and D is ethylene.

The product is a cyclic amidine in in which R individually is a member of the class consisting of tertiary-alkyl of 4 to 24 carbon atoms, phenyl, naphthyl, benzyl and alkyl substituted phenyl, naphthyl and benzyl in which the total alkyl substituents contain up to 16 carbon atoms;

R individually is a member of the class consisting of hydrogen and alkyl of 1 to 24 carbon atoms;

R and R collectively form a ring, with the nitrogen atom to which they are joined, from the class consisting of morpholino, thiamorpholino, piperidino and pyrrolidinyl;

R is a member of the class consisting of hydrogen,

2-hydroxyethyl, Z-aminoethyl, 3-hydroxypropyl, 3- aminopropyl, 2-(2-aminoethyl)aminopropyl, 3-(2- aminopropyl) aminopropyl, 2-(2-aminoet-hyl) aminoethyl and 2-(2-aminopropyl)aminoethyl;

X is a member of the class consisting of ethenylene,

ethylene, alkyl and alkenyl substituted ethylene having a total of up to 20 carbon atoms, 1,2-cyclohexylene, 1,2-cy'clohexenylene, alkyl substituted 1,2-cyclohexylene and 1,2-cyclohexenylene having a total of up to 16 carbon atoms, 3,6-methano-1,2-cyclohexylene and 3,6-methan-1,2-cyclohexenylene; and

D is a member of the class consisting of 1,2-cyclohexylene and a divalent saturated chain of 2 to 3 carbon atoms whose available valences are satisfied by members of the class consisting of hydrogen and alkyl and combinations thereof in which said alkyl have a total of up to 12 carbon atoms.

2. The cyclic amidine having the formula in which R represents tertiary alkyl of 4 to 24 carbon atoms; R; is hydrogen; R is hydrogen; X is ethylene and in which R represents tertiary alkyl of 4 to 24 carbon atoms; R5 is hydrogen; R is hydrogen; X is ethenylene and D is ethylene.

4. The cyclic amidine having the formula in which R represents tertiary alkyl of 4 to 24 carbon atoms; r

R is hydrogen;

R is 2-hydroxyethyl;

X is ethylene and D is ethylene.

5. The cyclic amidine having the formula D N h.

in which R represents tertiary alkyl of 4 to 24 carbon atoms; I

R is hydrogen;

R is 2-aminoethyl;

X is ethylene and D is ethylene.

6. The compound of claim 1 wherein R is tertiary alkyl averaging 18 carbon atoms; R is hydrogen;

R is 2-aminoethyl;

X is ethenylene and D is ethylene.

7. The compound of claim 1 wherein R is hexadecyl;

R is hexadecyl;

R is Z-aminoethyl;

X is ethenylene and D is ethylene.

8. The compound of claim 1 wherein R is tertiary alkyl averaging 18 carbon atoms; R is hydrogen;

R is hydrogen;

X is ethenylene and D is ethylene.

9. The compound of claim 1 wherein R is tertiary alkyl averaging 13 carbon atoms; R is hydrogen;

R is 2-aminoethyl;

X is ethenylene and D is ethylene.

10. The compound of claim 1 wherein R istertiary alkyl averaging 13 carbon atoms; R is hydrogen;

' R is 2-aminoethyl;

X is 1,2-cyclohexenylene and v D is ethylene.

11. The compound of claim 1 wherein R is phenyl;

R is hydrogen;

R is Z-aminoethyl;

X is dodecenylethylene and D is ethylene.

12. The cyclic amidine having the formula in which R represents tertiary octyl; R is hydrogen;

R is 2-aminoethyl;

X is ethylene and D is ethylene.

14. The compound of claim 1 wherein R is tertiary alkyl averaging 13 carbon atoms; R is hydrogen;

R is 2-hydroxyethyl;

X is ethylene and D is ethylene.

References Cited by the Examiner UNITED STATES PATENTS 2,640,055 5/1953 King et a1. 260-294.7 5 2,980,674 4/1961 Alberti et a1. 167-33 3,022,302 2/ 1962 Martensson 260-247.7

OTHER REFERENCES J ilek et 211.: Collection of Czechoslovak Chemical Communications, vol. 15, pp. 659-670 (1950). 10 Martensson: German application 1,122,958, February WALTER A. MODANCE, Primary Examiner. NATALIE TROUSOF, Assistant Examiner. 

1. THE CYCLIC AMIDINE HAVING THE FORMULA 